Ammonia → 9,9'-Spirobi[fluorene]-2-carbonitrile

HRID 1393794Notes

Reaction equation

HRID 1393794 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]3([C:26]4[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=4[C:20]4[C:15]3=[CH:16][CH:17]=[CH:18][CH:19]=4)[C:4]=2[CH:3]=1.[Cu][C:28]#[N:29].N>CN1C(=O)CCC1>[C:28]([C:17]1[CH:18]=[CH:19][C:20]2[C:21]3[C:26](=[CH:25][CH:24]=[CH:23][CH:22]=3)[C:5]3([C:4]4[CH:3]=[CH:2][CH:14]=[CH:13][C:12]=4[C:11]4[C:6]3=[CH:7][CH:8]=[CH:9][CH:10]=4)[C:15]=2[CH:16]=1)#[N:29]

Participants

5

Reactant 3

HCID 222AmmoniaHCID 152875222-Bromo-9,9'-spirobi[9H-fluorene]HCID 178418546HCID 178418546, compound

Product 1

HCID 231503269,9'-Spirobi[fluorene]-2-carbonitrile

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
160 °C

Procedure

A suspension of 158.1 g (0.4 mol) of 2-bromo-9,9′-spirobifluorene and 89.6 g (1 mol) of copper(I) cyanide in 1100 ml of NMP was heated to 160° C. for 16 h. After cooling to 30° C., the mixture was admixed with 1000 ml of saturated ammonia solution and stirred for a further 30 min. The precipitate was filtered off with suction, washed three times with 300 ml of saturated ammonia solution and three times with 300 ml of water, and suction-dried. After the solid had been dissolved in 1000 ml of dichloromethane, the solution was dried over sodium sulfate, filtered through silica gel and concentrated to dryness. The thus obtained crude product was recrystallized once from dioxane:ethanol (400 ml:750 ml). After the crystals had been dried under reduced pressure at 80° C., 81.0 g (237 mmol), corresponding to 59.3% of theory, were obtained.

Workup

  1. temperatureAfter cooling to 30° C.
  2. filtrationThe precipitate was filtered off with suction
  3. washwashed three times with 300 ml of saturated ammonia solution and three times with 300 ml of water
  4. customsuction-dried
  5. dissolutionAfter the solid had been dissolved in 1000 ml of dichloromethane
  6. dry with materialthe solution was dried over sodium sulfate
  7. filtrationfiltered through silica gel
  8. concentrationconcentrated to dryness
  9. customThe thus obtained crude product
  10. customwas recrystallized once from dioxane
  11. customAfter the crystals had been dried under reduced pressure at 80° C.
  12. custom81.0 g (237 mmol), corresponding to 59.3% of theory, were obtained

Sources & evidence

ORD record
ord-57622e2414444fef848a10b669d82295
Source dataset
uspto-grants-2008_03
Patent number
US07345301B2

Reaction notes

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